High-gloss room temperature curable water-based mold release agent

ABSTRACT

A room temperature curable water-based semi-permanent mold release agent is provided that is effective to facilitate the release of multiple successively molded polymer (such as polyester) parts following a single application of the mold release agent to the mold surface. The mold release agent preferably is effective to set within 1 hour of application to a mold release surface at 5-40° C., and to cure at the same temperature within 1-8 hours of application. The mold release agent is substantially devoid of VOCs, and therefore has no flash point.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to mold release agents. More particularly,it relates to a semi-permanent water-based mold release agent.

2. Description of Related Art

Molding is a well known technique for producing finished parts made fromplastics, polyester and other polymeric materials. Currently, moldedparts range from bicycle helmets to boat hulls to telephone receiverhandsets and beyond.

Molding is performed by processing (e.g. pouring, injecting, spraying,etc.) a liquid resin, or a reinforcing material (such as fiberreinforcing material) and a liquid resin, into a mold cavity or onto amold surface and then curing the resin to provide a finished solid partconforming to the cavity or surface. In order to prevent the finishedmolded part from sticking to the mold surface, a mold release agent isapplied to the surface prior to pouring the resin.

There are two basic types of mold release agent, sacrificial andsemi-permanent. A sacrificial mold release agent is one that is consumedor otherwise completely depleted after a single molded part is made inthe mold, and must be reapplied prior to making each molded part. Forthis reason, sacrificial mold release agents are costly and cumbersometo use.

Semi-permanent mold release agents are also applied to the mold surface.They can be of the wipe-on or spray-on type. These release agents arepreferred because they are not completely depleted following a singlemolding operation. A single semi-permanent mold release agentapplication can be used to facilitate the release of multiple successivemolded parts without reapplication of the release agent; e.g. up to 5,10, 15, 20, 25, 30 or more releases.

Conventionally, room temperature curing semi-permanent mold releaseagents, e.g. for room temperature molding applications (epoxy-based orpolyester-based composites), have been solvent based; that is theycontain significant amounts of volatile organic compounds (VOCs), andhave relatively low flash points and high vapor pressures. Existingsolvent based mold release agents present significant health and safetyhazards, both in use and transport.

There is a need in the art for a non-solvent based semi-permanent moldrelease agent, which is preferably water based, and does not suffer fromthe drawbacks mentioned above.

SUMMARY OF THE INVENTION

A mold release agent is provided. The mold release agent has 0.003-2weight percent amine-functional silicone and 0.001-2 weight percenthydroxy-functional silicone. The amine- and hydroxy-functional siliconesare dispersed in a water carrier phase.

A mold release agent is also provided having at least one functionalsilicone dispersed in a water carrier phase, where the mold releaseagent is substantially devoid of VOCs, and is effective to set at 5-40°C. within 1 hour after being applied to a mold surface.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE INVENTION

As used herein, when a range is given such as 5-25, that meanspreferably at least 5, and separately and independently, preferably notmore than 25. As used herein, the term solvent refers to organicsolvents. Also as used herein, the term functional silicone refers to asilicone chain, such as a siloxane chain, that has a functional groupbonded to at least one of the Si atoms in the chain. For example, ahydroxy-functional silicone is a chain having at least one —OH groupbonded to a Si atom in the chain; an amine-functional silicone is achain having at least one —NH₂ group bonded to a Si atom in the chain;etc. Other functional groups, including alkoxy, carboxy, etc., are knownin the art which can be bonded to a Si molecule in a silicone chain toprovide a functional silicone as that term is used herein. Preferably, afunctional silicone is at least bi-functional, meaning that there are atleast two functional groups bonded to the same (preferably different)silicon atom(s) in the silicone chain. Alternatively, the functionalsilicone can be multi-functional (3+ functional groups). Strongly lesspreferred are mono-functional silicones (only 1 functional group bondedto the silicone chain).

From the above, it will be understood that as used herein and in theclaims, the term hydroxy-functional denotes a hydroxyl group bonded to asilicon atom of a silicone or siloxane chain, and therefore is the samestructure as silanol-functional, ie. Si—OH. Unless otherwise explicitlyindicated, all percents herein are weight percents.

A water based mold release agent is provided. The invented mold releaseagent preferably has an amine-functional silicone and ahydroxy-functional silicone, and is a water-based silicone emulsion. Theinvented mold release agent preferably includes the following componentslisted in Table 1. Additional components not listed in Table 1 may alsobe included in the mold release agent according to the invention, aswill become more apparent below. All figures in Table 1 are weightpercents. In Table 1, any less preferred or more preferred concentrationor range for any one component can be combined with any other lesspreferred or more preferred concentration or range of any of the othercomponents to provide the mold release agent; it is not required thatall of the concentrations or ranges for all of the components come fromthe same column.

TABLE 1 Composition of water based mold release agent ComponentPreferred Less Preferred Less Preferred Amine-functional 0.045-0.06 0.027-0.2 0.018-1 silicone 0.03-0.075 0.024-0.5   0.015-1.5 0.029-0.1  0.021-0.8 0.003-2 Hydroxy-functional 0.01-0.015 0.008-0.2 0.005-1silicone 0.009-0.018  0.007-0.5   0.004-1.5 0.008-0.1   0.006-0.80.001-2 Slip agent 0.3-1    0.2-1.5    0-2

Preferably, the silicones used in the present invention (e.g. amine- andhydroxy-functional silicones) are siloxanes, and have a molecular weightin the range of 1,000-70,000, less preferably 1,000-100,000, lesspreferably 1,000-300,000, less preferably 1,000-500,000, less preferably1,000-700,000, less preferably 1,000-1,000,000, less preferably1,000-1,500,000, less preferably 1,000-2,000,000. Preferably, the moldrelease agent according to the invention has 1.5-2, less preferably1-2.5, less preferably 0.8-2.8, less preferably 0.5-3, less preferably0.4-5, less preferably 0.1-10, weight percent total nonvolatile solids,and a pH of 8-8.5, less preferably 7-8.8, less preferably 6-9, lesspreferably 5-9.2, less preferably 4.5-9.5, less preferably 4-10. Withrespect to nonvolatile solids content, the amount of solids is selectedbased on the type of molded part requiring mold release. Lower solidscontent, such as about 0.2%, can be used for easier release, whereashigher solids content, typically 5-10%, may be used to meet highperformance requirements.

The most preferred amine-functional silicone source is GP-50-A,available from Genesee Polymers Corp. GP-50-A is a water-based emulsioncontaining an amine-functional silicone (CAS No. 71750-80-6) in anamount of about or less than 3 weight percent. When GP-50-A is used, onemust take into account the concentration of amine-functional siliconepresent in GP-50-A and perform the appropriate calculation in order tosupply the correct amount of GP-50-A to ensure the correct weightpercent of amine-functional silicone from Table 1. This calculation iswell within the level of ordinary skill in the art. The most preferredhydroxy-functional silicone source is SEM500, available from Silchem,Inc. SEM500 is a water-based emulsion containing a hydroxy-functionalsilicone (CAS No. 556-67-2) in an amount of about or less than 1 weightpercent. When SEM500 is used, a similar calculation must be performed asdescribed above to provide the appropriate amount of hydroxy-functionalsilicone from Table 1.

Though GP-50-A and SEM500 are preferred for supplying the amine- andhydroxy-functional silicones respectively, other amine- andhydroxy-functional silicones can be used from other suitable non-solventbased sources or emulsions.

The slip agent from Table 1 most preferably is or includes nonfunctionalsiloxanes which can be straight-chain or branched. Alternatively, theslip agent can be one or a combination of functional siloxanes, wherethe functional groups are selected so as not to interfere with thefilm-forming or cross-liking mechanisms of the amine- andhydroxy-functional silicones, which are described in detail below. Forexample, such non-reactive functional groups include aromatics, vinylgroups, and alkane groups such as methyl, ethyl, propyl, etc. Lesspreferably, other known or conventional slip agents can be used.

In addition to the components listed in Table 1, the invented moldrelease agent also can be provided with other components to achievedesired physical and/or chemical characteristics, which components couldbe selected by a person having ordinary skill in the art without undueexperimentation based on the particular characteristic desired, and mayinclude emulsifiers, wetting agents, surfactants, solubilizers, organicor inorganic acids or bases to regulate pH, other silicones orsiloxanes, etc.

Preferably, the invented water based mold release agent is prepared fromthe above-mentioned preferred formulations and water by blending thecomponents at ambient temperature, e.g. 5-40, preferably 22-27,preferably about 25°, C. GP-50-A is a white opaque liquid having a mildodor, a specific gravity of 0.99, and a boiling point of 100° C. It isdispersible in water and has no flash point. SEM500 is an odorless whiteliquid having a boiling point of 100° C., a freezing point of 0° C. anda specific gravity of 1.0. It is soluble in water (at 20° C.).

When GP-50-A and SEM500 are both used to supply the amine- andhydroxy-functional silicones, the mold release agent according to theinvention most preferably has the following composition

-   -   1.82 weight percent GP-50-A;    -   1.43 weight percent SEM500; and    -   balance water (tap water is acceptable).        The above composition corresponds to about 0.055 weight percent        amine-functional silicone and about 0.014 weight percent        hydroxy-functional silicone, taking into account the respective        silicone concentrations in GP-50-A and SEM500. This composition        has about 1.92 weight percent total nonvolatile solids, a pH of        8.36 and no flash point. Mean particle size for nonvolatiles has        been measured at 0.09-1.06 μm.

When GP-50-A and SEM500 are used according to a preferred embodiment ofthe invention, the following components are also supplied in addition tothe amine- and hydroxy-functional silicones: an emulsifier, a wettingagent and an emulsion solubilizer. Each of these three components fallswithin the broad category of surfactants, the emulsifier having an HLB(hydrophile-lipophile balance) number in the range 8-18, the wettingagent having an HLB number in the range 7-9, and the solubilizer havingan HLB number in the range 15-18. The resulting composition is anoil-in-water emulsion which, when applied to a mold surface, coalesceson the surface to produce a thin film having a thickness of less thanabout 1 micron. The coalescence and film formation mechanisms aredescribed in greater detail below. The wetting agent facilitates uniformcoating onto the mold surface, though some excess may need to be wipedaway following a heavy coating of the mold release agent. Hydroxyltriazine (supplied in GP-50-A as less than about 0.5 weight percenthexahydro-1,3,5-tris(2-hydroxyethyl)-S-triazine, CAS No. 004-719-04-4)is provided in the mold release agent composition and is effective topromote or assist room temperature film formation as described below.The solubilizer provides freeze-thaw stability to the mold releaseagent, preferably sufficient to withstand three or more freeze/thawcycles which may occur as a result of shipping or storage as duringwinter months.

Less preferably, amine- and hydroxy-functional silicones can be usedfrom other sources, so long as suitable surfactants and/or wettingagents are also included to achieve effective wetting of the moldsurface, as well as effective silicone dispersion in the water carrierphase. Suitable surfactants and wetting agents are conventional in theart, or could be determined by a person of ordinary skill in the artwithout undue experimentation. Less preferably, other functionalsilicones could be used, e.g. alkoxy-functional silicones,carboxy-functional silicones and mixtures or combinations thereof.

As will be apparent from the above description, the mold release agentaccording to the invention preferably is prepared as a mixture of twopre-emulsions; an amine-functional siloxane emulsion (preferablyGP-50-A), and a hydroxy-functional siloxane emulsion (preferablySEM500). Preferably, the amine-functional siloxane emulsion contains thetriazine reagent described above (as does GP-50-A). Also preferably, thehydroxy-functional siloxane emulsion contains ethoxylated andoctylphenoxy types of surfactants (as does SEM500, which includes 1-5%octylphenoxypoly-ethoxyethanol, CAS No. 9002-93-1, and 1-5% ethoxylatednonyl phenol, CAS No. 9061-45-9). It will be understood that whenGP-50-A and SEM500 are not used, the components listed above may beseparately obtained and combined via conventional techniques to providethe respective amine- and hydroxy-functional siloxane pre-emulsions,which can then be blended as otherwise described herein to provide themold release agent according to the present invention. Care must betaken, however, to perform the appropriate calculations so the finishedmold release agent includes the appropriate amount of triazine materialand the above-mentioned surfactants based on their respectiveconcentrations in the GP-50-A and SEM500 emulsions, and the relativeamounts of these emulsions required to provide the appropriateconcentrations of amine- and hydroxy-functional silicones as listed inTable 1 above. These calculations are well within the level of ordinaryskill in the art.

The invented mold release agent has no flash point and is not flammableor combustible. The mold release agent is preferably devoid orsubstantially devoid of VOCs. Therefore, the invented water based moldrelease agent does not present any significant health or safety hazards,either in use or in transport. For example, the invented water basedmold release agent preferably can be shipped via standard carriers oreven by mail without arranging special shipping due to the presence ofdangerous VOCs or other dangerous properties, such as high flammabilityand low flash point which are characteristic of solvent based moldrelease agents.

The invented water based mold release agent preferably is coated on thesurface of a mold, preferably via wiping, less preferably spraying, andsets at ambient temperature (5-40, preferably 22-27, preferably about25°, C.) within 48, preferably 24, preferably 16, preferably 12,preferably 8, preferably 6, preferably 4, preferably 2, preferably 1,preferably 0.5, preferably 0.25, hours. After the invented mold releaseagent is applied, it has been found that water will evaporate at asatisfactory rate (i.e. within the time periods stated above) at roomtemperature without the addition of a volatilizer such as alcohol. Thisis an important benefit because molding of certain polymer resinsparticularly polyester molding) is carried out at room temperature, andtherefore most molds are not equipped with heating elements that couldbe used to set or cure the mold release agent. In addition, becausemolding is carried out at room temperature, the molds themselvestypically are not designed to withstand thermal cycling and could becomebrittle or even crack if cyclically heated to set the mold release agentafter application.

The invented mold release agent provides effective release (demolding ofmolded parts) while maintaining high gloss for both the mold surface andthe molded parts. This result is achieved via a dual-mode process. Thefirst mode is film formation: Once the release agent is applied to themold surface, the water phase (which is the bulk fluid phase) begins toevaporate. As the water evaporates, adjacent siloxane micelles in therelease agent collide as their fluid medium is diminished. Thesecollisions result in siloxane coalescence which generates a siloxanematrix in the form of a film on the mold surface. This matrix is boundto the mold surface via the functional groups (preferablyamine-functional and hydroxy-functional groups) of those siloxanemolecules located nearest to the mold surface. This film-formationprocess occurs relatively quickly compared to curing (described below),preferably within 10-60 minutes. As used herein and in the claims, themold release agent is understood to “set” as mentioned in the precedingparagraph when the just-described film formation process (via micellecoalescence) is substantially complete at the mold surface, preferablywithin about 15 minutes (0.25 hours) after application of the moldrelease agent at room temperature.

The second mode is curing, which is essentially cross-linking ofsiloxane molecules. Cross-linking proceeds relatively slowly, taking1-8, preferably 1-4, preferably 1-2, hours. The overall process is asfollows: First the film forms to provide a uniform structural matrix inwhich the cross-linked siloxane molecules will be supported upon curing.Next, curing occurs at a slower rate, and results in a highlycross-linked siloxane filled coalescent silicone matrix film layeradhered to the mold surface. The combination of the coalescent matrixfilm layer and the interspersed cross-linked siloxanes provides a highlyeffective mold release layer at the mold surface that provides excellentmold release characteristics for multiple successive molded partsfollowing the initial application of the mold release agent. High glossof both the mold surface and the surfaces of molded parts is alsoachieved. It has been found that both the mold surface and the surfacesof molded parts exhibit a gloss rating above 80 specular gloss unitsaccording to ASTM D523-89(1999) (described below).

Preferably, the invented mold release agent is applied to a mold surfaceas follows. For initial application, i.e. to a virgin mold surface orone that recently has been cleaned, the mold release agent is preferablyapplied by wiping (less preferably spraying) multiple coats onto themold surface. Preferably, when applied by wiping, the mold release agentis applied using a soft cloth that has been dampened with the moldrelease agent. The mold surface is then wiped uniformly to provide acoat of the mold release agent. Following awaiting period (preferably5-60, preferably 10-30, preferably about 15, minutes), a dry soft clothis used to wipe away excess mold release agent from the mold surface.Then a second coat is applied with the damp cloth as before. Again,following the waiting period, the excess is wiped away and the processis repeated. For initial application, this process is repeated toprovide preferably 2-10, preferably 3-8, preferably 4-6, coats of moldrelease agent to the mold surface. After a number of releases,preferably 10, 20, 30, 40, 50 or more releases, a touch up coat of themold release agent can be applied if release performance is diminished,for example if release becomes difficult. For a touch up coat,preferably only one coat of the mold release agent is applied asdescribed above. However, 2, 3, or 4 coats can be applied for a touch-upcoat if necessary. The interval and number of mold release agent coatsfor the touch-up coats is determined by the particular mold (e.g. sizeof molded part and material) to provide continued effective mold releaseand high gloss.

In addition to successful mold release, the invented water based moldrelease agent also resulted in molded parts (and the mold surface)having high gloss even after multiple successive releases followingextended periods of storage. The following examples are illustrative. Inthese examples, gloss was measured according to ASTM D523-89(1999)Standard Test Method for Specular Gloss (incorporated herein byreference), and is reported in standard specular gloss units whose scaleranges from 0-100. Above 70 gloss units is considered glossy, and values70 or below are considered semi-gloss.

EXAMPLES Example 1

Five mold release agent compositions according to the invention wereprepared as described above, having the following compositions listed inTable 2:

TABLE 2 Compositions of Mold Release Agents Nos. 1-5 for ReleaseExperiment Component Agent 1 Agent 2 Agent 3 Agent 4 Agent 5 GP-50-A1.82 1.82 2.27 2.73 3.64 SEM500 1.43 2.0 — — — SM2245 — — 2.0 2.0 2.0Water Balance Balance Balance Balance Balance Corresponding chemicalcompositions Amine-functional 0.055 0.055 0.07 0.082 0.11 silicone (CASNo. 71750-80-6) Hydroxy-functional 0.014 0.02 — — — silicone (CAS No.556-67-2) Hexahydro-1,3,5-tris(2- 0.009 0.009 0.0113 0.014 0.018hydroxyethyl)-S-triazine Dimethhyl polysiloxane — — 0.9 0.9 0.9 silanol(CAS No. 70131-67-8) Polymethylhydrogen — — 0.06 0.06 0.06 siloxane (CASNo. 63148-57-2) Octylphenoxypoly- 0.043 0.06 — — — ethoxyethanolEthoxylated nonyl phenol 0.043 0.06 — — —

Table 2 first lists the names and proportions of the commercialformulations used to prepare each of the five mold release agents(Agents 1-5). Second, the resulting chemical compositions are providedunder the heading “Corresponding chemical compositions.” In Table 2,italicized values are estimates based on the published compositions ofthe respective commercial formulations. GP-50-A and SEM500 havecompositions as already described above. SM2245 is a silicone emulsionavailable from GE Silicones having the following reported composition:1-5% propylene glycol, <1% formaldehyde, 30-60% dimethyl polysiloxanesilanol (a hydroxy-functional siloxane), 1-5% vinyl alcohol, and 1-5%polymethylhydrogen siloxane, balance water.

Each of the release agents listed in Table 2 was applied via wiping to amold surface used to mold gelcoat (polypropylene/polystyrene) parts atlow temperature (below 80° C.). First, the mold surface was cleaned byconventional techniques. Then an initial application (film) of the moldrelease agent was applied as follows: wiping on a coating, waiting about15 minutes to allow the water to evaporate, and then wiping away excessmaterial from the surface. This procedure was repeated 2-6 times foreach mold depending on the condition of the mold surface. The resultingmold release film was allowed to cure for 30 minutes. Next, twentysuccessive gelcoat parts were molded using the treated mold surface andthen released (demolded). No touch up coat of mold release agent wasapplied between any of the successively molded/demolded parts. Speculargloss for both the molded part surface and the mold surface weremeasured according to ASTM D523-89(1999). Ease of release was alsomeasured based on a scale from 1-6 where the following release valuescorrespond roughly to the stated amount of release force necessary tofacilitate demolding a finished molded:

-   -   6—release force of 0-0.005 N/cm² (mold and molded part undamaged        following release)    -   5—release force of 0.005-0.15 N/cm² (mold and molded part        undamaged following release)    -   4—0.15-0.35 N/cm² (mold and molded part undamaged following        release)    -   3—greater than 0.35 N/cm² (mold and molded part undamaged        following release)    -   2—greater than 0.35 N/cm² (molded part damaged or broken during        release)    -   1—greater than 0.35 N/cm² (total failure; mold damaged or broken        during release)

Specular gloss performance for the mold release agents according to theinvention was compared to that obtained using the conventionalsolvent-based room temperature cured mold release agent, WOLO™, which iswell known in the art and is available from Henkel Loctite Corporation.The results are listed below in Tables 3-5. In Tables 3-4, values arestandard specular gloss units (scale 0-100) from ASTM D523-89(1999), andin Table 5, values are in the above-described release quality scale of1-6.

TABLE 3 Specular gloss of mold surface for Agents 1-5 for twentysuccessively molded and released gelcoat parts Release No. Agent 1 Agent2 Agent 3 Agent 4 Agent 5 WOLO ™ Bare mold 96.3 96.2 94 94.4 96 94.7surface (no mold release agent)  1 92.9 91.2 94 91.8 89 80.3  2 94.390.2 89 88.1 89.9 75.6  3 92.9 90.9 81 89.3 86.5 74.3  4 92.1 93 85.583.3 84.2 69.7  5 93.9 91.6 84 80.3 78.8 65.8  6 83.6 91 83.6 77.1 74.768.3  7 91.9 90.2 83.2 67.7 73.9 64.3  8 87.8 88.4 83.4 75 81.4 56  991.9 88.4 82.6 77.6 76.1 56.2 10 89.6 89.8 78.5 73.7 80.2 57.7 11 92.286.2 81.2 70.8 75.6 58.1 12 81.5 79.4 86.5 75 70.2 55.6 13 82.1 84 79.264.9 74.1 52.9 14 84.3 83.4 85.9 74 75.8 53.4 15 87.1 80.3 72.7 66.371.4 50.8 16 90.2 83.8 84.1 73 75.2 48.9 17 88.2 81.9 82.8 65.4 76.249.2 18 84.8 82.6 79.1 67.3 69.7 47.6 19 86.4 85 80.6 66.6 68 42.1 2089.3 85.2 78 63.2 73.4 44.2 Average = 88.8 86.8 82.7 74.5 77.2 58.5 Last5 avg = 87.8 83.7 80.9 67.1 72.5 46.4

TABLE 4 Specular gloss of molded part surfaces for Agents 1-5 for twentysuccessively molded and released gelcoat parts Release No. Agent 1 Agent2 Agent 3 Agent 4 Agent 5 WOLO ™  1 87.8 84.7 85.2 84.4 80.9 86.9  292.9 87.6 85.3 81.9 88.4 84  3 89.3 86.7 84.5 87.2 86.3 81.3  4 92.892.4 86.5 82.7 88 81.5  5 93.1 88.2 85.4 82.7 81.8 73.1  6 92.9 91.385.5 80 67.3 74.5  7 90.6 92.1 84.4 75.3 71 70.9  8 91.1 87 83.3 78.481.6 62.7  9 92.2 91 84.3 75.5 78.6 61.8 10 91.9 91.7 81.5 75.2 78.6 6211 92.1 86.3 82.7 73.5 81.1 64.5 12 91.1 88.2 81.5 71.5 75.4 58.5 1389.1 92.5 82.8 65.8 81.9 60.4 14 90.9 91.4 85 70.2 84.9 61.8 15 87.184.1 79.7 68.4 71.4 54.1 16 88.1 86.2 81.4 71.5 73.1 57.7 17 88.7 80.680.3 67.3 61.9 52.9 18 91.9 89.6 84.8 67.6 70.2 51.7 19 90.4 84.5 81.170.7 74.9 51.1 20 88.1 88.4 74.2 69.6 67.7 47.6 Average = 90.6 88.2 83.075.0 77.2 64.9 Last 5 avg = 89.4 85.9 80.4 69.3 69.6 52.2

TABLE 5 Release quality for Agents 1-5 for twenty successively moldedand released gelcoat parts Release No. Agent 1 Agent 2 Agent 3 Agent 4Agent 5 WOLO ™  1 5 5 5 5 6 6  2 5 5 5 5 5 6  3 4 6 5 5 5 6  4 5 5 6 5 56  5 5 5 5 4 5 6  6 5 5 5 4 5 6  7 4 5 4 4 4 5  8 5 5 4 5 5 5  9 5 5 5 55 6 10 4 4 4 4 4 5 11 5 5 5 4 5 5 12 5 5 5 5 5 5 13 4 5 5 5 5 5 14 4 4 54 5 5 15 5 5 5 4 4 5 16 4 4 5 4 4 5 17 4 4 4 4 4 6 18 5 5 5 5 4 5 19 5 55 4 4 5 20 5 5 4 4 5 5 Average = 4.6 4.8 4.8 4.8 4.7 5.4 Last 5 avg =4.6 4.6 4.6 4.6 4.2 5.2

From the data in Tables 3-4, one can see that the mold release agents(Agents 1-5) according to the invention resulted in substantiallysuperior specular gloss results for both the mold surface and thesurfaces of successively molded parts over twenty consecutive moldingsand releases. In particular, Agents 1-5 resulted in substantiallysuperior specular gloss for both the mold surface and the surfaces ofmolded gelcoat parts for the last five releases (release nos. 16-20.This demonstrates the superior efficacy of the non-solvent-based moldrelease agents according to the invention to provide superior glossfollowing a large number of mold releases after only an initialapplication of the mold release agent. In addition to superior glosscharacteristics, Agents 1-5 provided comparable mold release performanceto the conventional WOLO™ solvent-based agent.

Example 2

Mold release agents 1, 2, 3 and 5 from Table 2 of Example 1 above weresubjected to an experiment measure release and specular glossperformance following one year of shelf life. Each of these agents wasprepared and then placed in an oven and maintained at a constanttemperature of 45-46° C. It has been found that one day of storage atthis temperature results in comparable aging (such as by decomposition)to about 9 days of storage under ambient conditions. Thus, 40 days ofstorage at this temperature was used to simulate one year of shelfstorage. Results are provided in Tables 6, 7 and 8 below. Values inTables 6-8 are reported in the same units as in Tables 3-5 respectively.

TABLE 6 Specular gloss of mold surface for Agents 1, 2, 3, and 5 fortwenty successively molded and released gelcoat parts after 1-year shelflife Release No. Agent 1 Agent 2 Agent 3 Agent 5  1 89 91.8 87.2 87.1  284.5 92.4 87.2 86.2  3 86.1 90.9 85.1 85.4  4 86 91.5 83.3 84.1  5 82.486.8 80.7 81.2  6 84.3 87.1 81.3 83.9  7 84.6 89.8 81.9 84  8 83.9 89.381.9 82.7  9 88.8 91.2 84 83.8 10 86 90.8 84 86 11 83.3 88.4 82.5 81.512 84.8 88.8 80.1 81.2 13 88 89.4 82.4 84.8 14 85.3 88 82 82.6 15 87.789.9 81 82 16 84.1 89.1 80.5 80.8 17 84.2 88.4 81.8 82.7 18 85.1 88.481.1 82 19 83 85.6 79 80.7 20 87.5 89.7 85.5 83.4 Average = 85.4 89.482.6 83.3 Last 5 avg = 84.8 88.2 81.6 81.9

TABLE 7 Specular gloss of molded part surfaces for Agents 1, 2, 3, and 5for twenty successively molded and released gelcoat parts after 1 yearshelf life Release No. Agent 1 Agent 2 Agent 3 Agent 5  1 82.9 82.3 80.378.9  2 89.7 89.6 86.5 83.9  3 90.1 90.7 87.6 85.9  4 89.7 92.2 89.189.4  5 84.5 91.1 86.1 89.2  6 88.9 90.7 86.9 87.6  7 89.7 90.8 87.289.3  8 89.3 90.6 87 88.9  9 89.6 90.6 86.7 88.8 10 89.4 90.6 86.7 86.611 87.6 88.7 84.6 86.7 12 87.4 90 85.1 86.6 13 88 89.4 85.5 85.9 14 85.389.8 85 85.5 15 87.2 89.3 84.5 86.5 16 86 88.8 83.8 86.5 17 88.7 89.487.3 88.5 18 87.5 88.3 85.5 86.8 19 88.8 89.6 85.2 85.9 20 89.5 91.287.9 86 Average = 88.0 89.7 85.9 86.7 Last 5 avg = 88.1 89.5 85.9 86.7

TABLE 8 Release quality for Agents 1, 2, 3, and 5 for twentysuccessively molded and released gelcoat parts after 1 year shelf lifeRelease No. Agent 1 Agent 2 Agent 3 Agent 5  1 4 4 5 5  2 5 5 4 5  3 5 45 5  4 5 5 5 5  5 5 5 5 5  6 5 5 5 5  7 5 5 5 5  8 5 5 5 5  9 5 5 5 5 105 5 5 5 11 5 5 5 5 12 5 4 5 4 13 5 4 5 5 14 4 4 5 4 15 5 4 5 4 16 4 4 44 17 4 4 4 4 18 5 4 5 4 19 5 5 5 5 20 5 5 4 5 Average = 4.8 4.5 4.5 4.7Last 5 avg = 4.6 4.4 4.4 4.4

Comparing the data in Tables 6-8 with the analogous data in Tables 3-5,mold release agents 1, 2, 3, and 5 from Table 1 exhibited virtually nodecline in performance following a simulated one year shelf life. Theinvented mold release agent's ability to provide substantially the samesuperior specular gloss performance following a one year shelf life asfor zero shelf life was a highly surprising result.

As can be seen from the above examples, both the molded parts and themold surface itself consistently exhibited gloss unit values above 80even after 20 successive releases following one year (simulated) ofstorage of the mold release agent. This also was a highly surprising andunexpected result.

Surprisingly, the invented water based mold release agent providescomparable mold releasability, and superior gloss following multiplesuccessive releases compared to existing solvent-based, room temperaturecuring mold release agents, particularly for gelcoat molded parts. Yet,the invented mold release agent is room temperature curable, issubstantially devoid of VOCs, has no flash point and is substantiallynon-flammable and non-combustible.

Although the above described embodiments of the invention constitute thepreferred embodiments, it should be understood that modifications can bemade thereto without departing from the scope of the invention as setforth in the appended claims.

1. A mold release agent comprising 0.003-2 weight percentamine-functional silicone, 0.001-2 weight percent hydroxy-functionalsilicone, and a triazine material in a water carrier phase, and a slipagent in an amount of about or less than 2 weight percent wherein thetriazine material is present in an amount effective to promote roomtemperature film formation from said mold release agent followingapplication thereof to a mold surface.
 2. A mold release agent accordingto claim 1 ,having a ph of 4-10.
 3. A mold release agent according toclaim 1, being effective to set at 5-40° C. within 48 hours after beingapplied to a mold surface.
 4. A mold release agent according to claim 1,being substantially devoid of VOCs.
 5. A mold release agent according toclaim 1, having no flash point.
 6. A mold release agent according toclaim 1, wherein said hydroxy-functional silicone is provided from awater based emulsion.
 7. A mold release agent according to claim 1,wherein said amine-functional silicone is provided from a water basedemulsion.
 8. A mold release agent according to claim 1, being effectiveto facilitate at least 10 successive effective releases of molded partsfrom a mold surface following initial application of said mold releaseagent to said mold surface.
 9. A mold release agent according to claim1, further comprising at least one component selected from the groupconsisting of alkoxy-functional silicones and carboxy-functionalsilicones.
 10. A mold release agent according to claim 1, beingeffective to provide specular gloss to a mold surface of at least 70specular gloss units according to ASTM D523-89 (1999) after 10consecutive mold releases from said mold surface following initialapplication of said mold release agent to said mold surface.
 11. A moldrelease agent according to claim 1, being effective to provide speculargloss to a mold surface of at least 80 specular gloss units according toASTM D523-89 (1999) after 10 consecutive mold releases from said moldsurface following initial application of said mold release agent to saidmold surface.
 12. A mold release agent according to claim 1, beingeffective to cure at 5-40° C. within 1-8 hours after being applied to amold surface.
 13. A mold release agent according to claim 1, saidtriazine material being present in an amount of 0.009-0.018 weightpercent.
 14. A mold release agent according to claim 1, said moldrelease having 1-2.5 weight percent non-volatile solids and comprising0.03-0.075 weight percent amine-functional silicone, 0.009-0.1 weightpercent hydroxyl-functional silicone.
 15. A mold release agent accordingto claim 14, further comprising a wetting agent having an HLB numher of7-9, an emulsifier having an HLB number of 8-18 and an emulsionsolubilizer having an HLB number of 15-18.
 16. A mold release agentaccording to claim 14, said triazine material being hexahydro-1,3,5-tris(2-hydroxyethyl)-S-triazine.
 17. A mold release agent according to claim1, comprising about 0.55 weight percent amine-functional silicone andabout 0.014 weight percent hydroxyl-functional silicone, said triazinematerial being hexahydro-1,3,5-tris (2-hydroxyethyl)-S-triazine.
 18. Amold release agent according to claim 17, said mold release agent havinga total non-volatile solids content of 1-2.5 weight percent.
 19. A moldrelease agent comprising 0.003-2 weight percent amine-functionalsilicone, 0.001-2 weight percent hydroxyl-functional silicone, and atriazine material in a water carrier phase, said mold release agenthaving 0.1-10 weight percent total nonvolatile solids wherein thetriazine material is present in an amount effective to promote roomtemperature film formation from said mold release agent followingapplication thereof to a mold surface.
 20. A mold release agentaccording to claim 19, having a pH of 4-10.
 21. A mold release agentaccording to claim 19, said triazine material being a hydroxyl triazinematerial.
 22. A mold release agent according to claim 19, beingeffective to set at 5-40° C. within 48 hours after being applied to amold surface.
 23. A mold release agent according to claim 19, beingsubstantially devoid of VOCs.
 24. A mold release agent according toclaim 19, having no flash point.
 25. A mold release agent according toclaim 19, being effective to facilitate at least 10 successive effectivereleases of molded parts from a mold surface following initialapplication of said mold release agent to said mold surface.
 26. A moldrelease agent according to claim 19, further comprising at least onecomponent selected from the group consisting of alkoxy-functionalsilicones and carboxy-functional silicones.
 27. A mold release agentaccording to claim 19, being effective to provide specular gloss to amold surface of at least 70 specular gloss units according to ASTMD523-89 (1999) after 10 consecutive mold releases from said mold surfacefollowing initial application of said mold release agent to said moldsurface.
 28. A mold release agent according to claim 19, being effectiveto provide specular gloss to a mold surface of at least 80 speculargloss units according to ASTM D523-89 (1999) after 10 consecutive moldreleases from said mold surface following initial application of saidmold release agent to said mold surface.
 29. A mold release agentaccording to claim 19, said triazine material being present in an amountof 0.009-0.018 weight percent.
 30. A mold release agent according toclaim 19, said mold release having 1-2.5 weight percent non-volatilesolids and comprising 0.03-0.075 weight percent amine-functionalsilicone, 0.009-0.1 weight percent hydroxyl-functional silicone.
 31. Amold release agent according to claim 19, further comprising a wettingagent having an HLB number of 7-9, an emulsifier having an HLB number of8-18 and an emulsion solubilizer having an HLB number of 15-18.
 32. Amold release agent according to claim 19, said triazine material beinghexahydro-1,3,5-tris (2-hydroxyethyl)-S-triazine.
 33. A mold releaseagent comprising 0.003-2 weight percent amine-functional silicone,0.001-2 weight percent hydroxy-functional silicone, and a triazinematerial in a water carrier phase, said triazine material being ahydroxy triazine material wherein the triazine material is present in anamount effective to promote room temperature film formation from saidmold release agent following application thereof to a mold surface. 34.A mold release agent comprising 0.003-2 weight percent amine-functionalsilicone, 0.001-2 weight percent hydroxyl-functional silicone, and atriazine material in a water carrier phase, said triazine material beinghexahydro-1,3,5-tris (2-hydroxyethyl)-S-triazine wherein the triazinematerial is present in an amount effective to promote room temperaturefilm formation from said mold release agent following applicationthereof to a mold surface.